Beneficiation of iron ore



Patented Sept. 18, 1945 2,385,054 BENEFICIATION or mos oar:

Robert B. Booth, Springdale, and Earl C. Herkenhoil', Stamford, Conn,asslgnors to American Cyanamid Company, New York, N. Y., a corporationof Maine No Drawing; Application August 11, 1943, Serial No. 498,254

15 Claims.

This invention relates to the froth flotation of oxidized iron ores andmore particularly to processes using sulfonated organic carboxylic acidreagents.

The beneflciation of oxidized iron ore by froth flotation has presenteda peculiarly dimcult practical problem. It is a comparatively simplematter to concentrate certain oxidized iron ores by froth flotation witha large series of promoters, such as for example oleic acid; however,the economics of iron ore utilization are such that it is necessary toobtain both good iron recovery and a relatively high grade in order tomake the process economical because of the low price for which iron oreconcentrates sell.

According to thepresent invention oxidized iron ore is floated using asulfonated talloel reagent, preferably. in the presence of anunsulfonated oil, and for best results it is necessary to treat the ironore feeds with an acid substance the anion of which is capable offorming an acid having a dissociation constant greater than 10-".Commercial results are not obtainable without the acid treatment exceptwhen very highly sulfonated talloel is used, in which case the promoteritsell is probably sufliciently acid or gives off sufficient acid toeffect the necessary change on the surface of the iron ore particles.

Throughout the specification and claims the term sulfonated talloel willbe used in its usual commercial sense to cover the products obtainableby reacting talloel with strong sulfuric acid. It is quite possible thatboth sulfonation and sulfation take place, and it is not intended thatthe term sulfonated talloel shall be restricted to a compound in whichall. ordinary sulfur is present in the form of the sulfonic acid groups.

It is an advantage of the present invention that talloel which has beenfreed of lignin may be used;

and it is, of course, possible to use highly purified talloel obtainedby distillation and similar processes for refining talloel. Forpractical operation we prefer to use sulfonated refined talloel as theresults areslightly better than with the sulfonated crude product, andno material improvement is obtained when sulfonated distilled talloel isused, so that the higher cost of the latter product is normally notinstilled in commercial operation. This flexibility with regard to theconstitution of the reagent is of considerable importance becausetalloel is not a rigidly standardized chemical compound. 0n thecontrary, the exact composition of talloeis will vary depending on theparticular wood used in the sulfate paper process from which the blackliquor soap is obtained, the part of the country in which the treesoccur, and other factors. In our experience any of the widelydistributed commercial refined talloels may be sulfonated to produce areagent which will give satisfactory results in practical operation.While comparable results may be obtained with sulfonated refined orsemi-refined talloel and with sulfonated distilled talloel, it should benoted that the amount of sulfonation is not necessarily the same. Forexample, treating distilled talloel with a smaller amount of sulfuricacid will produce a product which behaves in a manner similar to asulfonated product obtained from reflned or semireflned talloel whichhas been treated with a larger amount of sulfuric acid. For example,distilled talloel treated with 30% by weight of sulfuric acid gives aproduct, the behaviour of which in the process of the present inventionclosely approximates that of ordinary refined talloel which has beentreated with 50% of sulfuric acid.

It is not necessary to isolate the sulfonated talloel. On the contrary,the reaction mixture itself may be used'or it may be partially or whollyneutralized with alkali. No material difference in flotation efliciencyis to be noted, and we believe that the impurities produced in thesulfonation reaction do not exert any deleterious effect on theflotation. The possibility of using crude sulfonation mixtures whichare, of course, cheaper is a valuable advantage or the presentinvention. Any economy in reagent cost is of considerable importance iniron ore flotation by reason of the low sales price of the finalproduct.-

It is a further advantage of the present invention that it is notlimited to sulfonated talloels produced by any particular sulfonationprocedure and any of the ordinary sulfonation processes may be used.

The sulfonated talloel reagent of the present invention is ratherdifferent in its characteristics from sulfonated petroleum hydrocarbonswhich are claimed in our copending applications, Serial No. 481,906,filed April 5, 1943, and Serial No. 491,384, filed June 18, 1943. Whilethe present invention shares with these other applications thepossibility of producing a commercially useful grade of iron oreconcentrate from practically any iron ore which is available, thebehavior toward acid neutralization and other factors is ratherdifferent. sulfonated petroleum hydrocarbons in general do not giveuseable results unless the iron ore is pre-treated with a fairly strongacid. sulfonated talloel may, however, be used alone or with additionalunsulfonated oils without pre-treatment with acid where highlysulfonated material is employed. n the other hand low sulfonated talloelwill'not give useful results with acid treated ore alone in the absenceof unsulfonated oils, and in fact with very low degrees of sulfonationthe acidtreatment may actually inhibit practical flotation. It is clearthat the froth flotation of iron ore using sulfonated re-,

agents with acid pre-treatment of the ore must involve a number offactors, the full extent of which has not yet been determined. Withoutdesiring to limit the present invention to any unproven theories webelieve that one reason for the anomalous results with talloel of lowdegree of sulfonation may lie in the fact that in such cases the majorportion of the promoter is in the form of an unsulfonated fatty acid orresin acid, and one of the drastic distinctions between sulfonatedreagents and carboxylic acid reagents is that acid pre-treatment of theore often-times inhibits flotation with the latter. i Anotherdistinguishing featuie between sulfonated talloel and sulfonatedhydrocarbons is that many of the latter give satisfactory results onacid pre-treated iron ore even though the flotation circuit may bebrought to neutrality or even slight alkalinity with ordinary alkalisuch as soda ash. With sulfonated talloel, however, commercial resultshave not been obtained unless the flotation circuit itself remains acid.

It is an advantage of the present invention that the particular acidused does not appear to be critical. although results of practicalutility are not obtained with weaker acids than those having adissociation constant oflfl- It is, of course. necessary that the acidanion should not have a known depressive effect on the iron ore.Sulfuric acid gives as good results as any, and because of its greatcheapness constitutes the preferred acid for practical operation. It is,however, not superior to other strong acids in the quality 'of theresults obtained and its choice is, therefore, dictated primarily byeconomic costs rather than operative efliciency.

It is an advantage of the present invention that satisfactory resultsare obtainable with sulfonated talloelalone when the ore has beenproperly pretreated with acid. However, the sulfonated talloel may, ofcourse, also be mixed with other sulfonated reagents such as sulfonatedpetroleum hydrocarbons and under some circumstances these mixed reagentspossess some economical. advan-' tages. It is also possible to combinean anionic float using sulfonatedtalloel with a silica float of theconcentrate using known cationic froth flotation procedures. Withordinary iron ores this double float does not give improved results and,therefore, its additional cost is not justifled. It is, however,available for the treatment of certain particularly refractory ores.

The froth flotation process of the present invention behaves normallywith respect to slime, that is to say in common with many anionicflotations a small amount of slime can be tolerated. but larger amountsof slime decrease grade of concentrate and increase reagent consumption.It is, therefore, desirable to deslimefairly thoroughly, although theextreme degree of deslimin which is essential with many cationicflotations is not necessary. Ordinary good desliming practice may,therefore, be followed, and it is an advantage of the present inventionthat the process is not critical in this respect. 4

The process of the present invention gives excellent results with themore common oxidized iron minerals such as hematite and magnetite. Itis, however, an advantage of the present invention that other ironminerals commonly present in iron ores, such as martite, limonite,siderite. goethite, and the like, may also ,be successfully floated bythe procedure of the present invention.

' The invention will be described in greater detail in conjunction withthe following specific examples which deal with the treatment of typicaliron ores. In some cases low grade iron ores are used which present amore difllcult problem in obtaining high grades with good recoveries.The parts are by weight.

Example 1 A low grade refractory Minnesota iron ore forming a rejectfrom iron beneflciation operations and containing about 15% Fe ashematite with some limonite mixed with a quartz gangue Promoter usedWith 1.62 lbsJton sulfuric With 1.62 lbsJton sulfuric sulionated talloelacid acid and an lba/ton 1...: oil

Concentrate Rgh. tail- Concentrete 11gb. teil- Concentrate Rgh. tail-Concentrate Rgh. tailpercent Fe ing percent Fe in: percent Fe inspercent Fe in Pm Parts talioel D's Assay Assay Du. Assay Db Assay an):$62 PH trib. we :1; PH an: 8.7.; Pa

Fe Fe is 100 None 31. 47 80. 26 8. 46 7. 1 No promotion 28. 48 64. 28 6.81 7. 1 No promotion 100 39. 33 62. 77 6. 60 6. 7 No useful 110st 61. 7146. 89 7. 08 6. 7 No useful float 100 2) 19. 94 89. 66 2. 76 6. 7 66. 3761. 34 ll) .8 42. 76 a0. 62 l. 71 6. 7 66.67 70. 84 4. l8 2. 8 1(1) 29.38 90. 36 1. 79 6. 6 49. 66 71. 09 82 2. 8 44. 42 92. 81 1. 01 6. 6 60.39 88.16 1. 91 2. 8 100 30. 93 87.38 2. 16 6. 4 48. 36 61. 28 07 2. 636. 83 92. 62 1. 43 6. 8 66. 23 90. 67 1.19 2. 7 100 60 37. 38 83. 86 2.39 6. 2 66. 61 72. I) 76 2. 8 43. 96 91. 70 l. 49 4. 6 62. 66 89.72 1.31 2. 6 100 60 36.23 91.87 1.31 6.3 43.71 $1.14 .46 2.6 63.92 94.76 0.724.3 66.48 94.39 0.83 2.6 100 70 64. 93 81. 27 2. 87 4. 0 63. 98 68. 8640 2. 6 62. 18 92. 76 0.96 4.0 66. 19 96. 0.- 42 2. 6 100 at 41.18 83.712.16 3.8 62.42 63.79 .06 2.7 66.77 93.09 0.89 3.8 67.60 92.86 1.07 2.6100 90 63.60 66.66 4.18 3.7 62.00 66.69 .3 2.7 67.74 86.62 1.79 3.867.66 89.06 1.66 2.6 100 100 60.07 38.33 7.40 3.6 69.69 36.16 76 2.668.46 69.01 3. 70 3.66 69.11 86. 27 1.73 2.6

Certain anomalous results will be noted where 20 as hematite associatedwith a quartz gangue; was

sulfonated talloel was used alone or with ore treated with sulfuric acidbut without any unsulionated oil. The 80% sulfonated talloel gave poorergrade than the 70% and in conjunction conditioned with 30% suli'onateddistilled talloel with and without added fuel oil, sulfuric acid andboth. The amount of sulfonated reagent was 2 lbs. per ton. The resultsappear in the followwith sulfuric acid the 60% was poorer than even 25ing table:

523% m, Sulfcnatd talloel alone with 25$ With 5.00 lbe./ton fuel oil iggggggggggg g gg a Concentrate Rgh. teil- Concentrate Rgh. tail-Concentrate Rgh. tail- Concentrate Rgh. tallpercent Fe ing percent Feing percent Fe in: percent Fe ing 61% "3}? my Amy A say Assay Assay mmpH Assay pH Assay at pH Assay a pH Fe Fe Fe 100 so 24.12 92.96 3.94 6.638.09 8.1.14 2.8 43.69 96.46 0.96 6.4 68. 91.% 2.16 3.8 100 20 B. 10 88.62 8. 80 6. 7 61. 16 4. 37 2. 8 100 10 38. 12 86. 44 4. 49 6. 8 N0 1138I11 float 100 None 39. 17 79. 87 6. 89 7. 1 No prolmotion the 20%. Thesegrade results are not significant where they fall unusually low, becausein the absence of unsulfonated oil the froth was very intense and anunusually low grade merely means that there was gangue carried alongmechanical- 1y. The adverse eflect of sulfuric acid in the case ofunsulfonated talloel or 10% sulfonated talloel has been discussed above,and we believe is due to the fact that in these cases the normal effectof acid with carboxylic acid promoters predominated.

Example 2 A somewhat higher grade Minnesota iron ore 5 sulfonatedtalloel.

Example 3 The ore of Example 1 was used to test sulfonation of differenttalloels. The conditioning and 50 notation procedure was the same as inExample 1.

The amount of sulfonated reagent usedwaa 1.62 lbs. per ton, except inthe cas of test 3, where it was 1.08, and test 7, where it was 1.36. Ineach case attempts were made to operate under opwasher tailing,containing about 25% Fe mainly timum conditions for the particulartalloel.

Concentrate Bo her Percentage sulionication LbsJton W at Fe Promoterused-type of talloel A at; Sulfuric acid Eff 1 3: m name. per pH cent FeA crude talloel containing lignin 100 3.23 1. 62 62. 66 90. 88 l. 01 2.7 Distilled tailoel-about 30% rosin acids 100 3. 2a 1. 62 64. 76 90.83 1. 19 2. 6 Distilled talloel 00 2. 28 1. c2 c2 30 so. so 1. e7 2 7Partial] refined Canadian talloel high in nonsaponiflable mater l 00 3.Z! 1. 62 69. 41 60. 06 6. 91 2. 6 A refined blown talloel m 3. 23 1. 6263. 74 93. 30 0. 88 2. 8 Partially refined talloel containing someprecipitated rosin 100 3. 23 l. 62 67. 71 90. 19 1. 38 2. 6 D0 00 3-231.62 60.46 89.66 1.36 2.6 Talloel-dlluted with 10% secondary butanol 1000 3. 06 l. 62 so. 64 88. 65 1.66 2. 7 Distilled talloel about 30% rosinacids.... v 100 gas 86% acid)... 3. 66 1. 62 65. 35 85. 84 i. 61 2. 0 D0100 oleum) 3.23 1.62 66.65 33.34 1.91 17 Refined talloel-aitersullonation neutralized to methyl orangewith causticsoda ...4...-. 00 60a 1.21 1.62 60.68 78.87 2.67 Distilled tall sulionation neutralized tomethyl orange with caustic soda 100 1 8% acid)..- 1. 21 1. 62 ea 70. 992. 57

in one case, did not give quite as good results as sulfonated ordinaryrefined tailoel. However, all of the talloels gave results which may beconsidered satisfactory.

Eeamplc 4 the case of saponified talloel. where 4 lbs. of

sulfuric acid were used. Conditioning procedure and flotation procedurewere identical with those of the two preceding examples. Themetallurgical results appear in the following table:

Concentrate Rougher tail- Addition reagent percent Fe m8 Distribu- TypeLbalton Assay "on pei ceent p11 Talloel 4.58 58.40 92.53 1.25 2.8 Oleicacid 4.47 59.23 91.00 1.91 Crude oil 5. 13 56. 48 95. 21 0.83 2. 8Chlorinated kerosene 3.88 30. 66 83. 93 3. 28 Coconut oil 3. 24 00. 0792. 14 1. 37 Cottonseed oil 3.03 59.47 80.12 2.15 Na htilenic acids. 4.11 56. 25 85.35 2. 45 neptaldehyde.. 4. 2o 54. 57 82. 70 2. 81 Methylester of talloel 4. 47 59. 59 84. 23 2. 89 Lauryl merca tan... 3. d 59.83 83. 68 3. 22 2 8 Sa nifled tal oel.- 4.00 55.89 90. 54 1.91 2. 6 B6,fuel oil 5. 02 58. 69 91. 90 2. 2. 8

It will be apparent that good results are obtainable with all of theunsulfonated oils and are commercial with the possible exception ofn-heptaldehyde where the concentrate was a little below usual commercialgrade. Excellent results are obtained with talloel and coconut oil asthe unsulfonated modifying agents. Good results are also obtainable withordinary fuel oil, and the choice will be determined largely by economicconsiderations, primarily the relative costs of the materials. The widechoice of cheap unsuifonated modifying agents represents an advantagebecause of the greater flexibility of the operation. It is of course,possible to use mixtures of unsulfonated oils where such mixtures may bedesirable for economic reasons.

Example 5 The It will be noted that some crude talloels gave g excellentresults and that distilled tailoels. except Concentrate m. an- Mm percent 1's in;

Fuel oil, H-M Type LbsJton Assay Pm. pH

1.02 4.0 50. 91. 2.15 3.8 1.52 0.80 50.37 90.51 0.00 2.9 2.10 3.48 56.8791.12 1.07 2.4 I 2.48 5. 50.71 78.05 0.45 0.0 s. as s. so so. 14 0c. 21use a. 9 3.90 180 57.50 94.24 1.10 4.0

2.10 3.50 50. 37 90.2) 0.88 3.0 4. 00 54. 57 90. 10 0- 95 0. 1 5.41 3.5442.77 90.00 1.07 0.5 3. 25 3. 54 59. 83 77. (I) 4. N 2. 9 3. 25 4. M 57.92 91. 72 1. 31 3. 3 3.25 3.80 58. 51 95.72 1.07 2.7 None 4. 07 43. 5990. 45 0. 95 0. 4

oil.

I Unsulionated tslloel used in place of fuel I Saturated.

preferred because of its cheapness. The figures for acid and fuel oilare based on are rather than deslimed feed which basis was used in thetable following Example 2.

Emmple 6 The flotation procedure of Example 1 and 2 was followed usingthe ore of Example 2. In each case a sulfonated refined talloel wasused, the first and third tests employing 3.34 lbs. per ton and thesecond test 4 lbs. per ton. Typical acid salts were used in place ofacids and the metallurgical results appear in the following table:

substantially the same results as sulfuric acid. but require largerquantities. Smaller quantities of sodium silico-fluoride may be usedwith some sacrifice of grade. In each case an amount of acig1 tsgalt wasused which was felt to give good res Example 7 The ore and flotationprocedure of Example 1 was followed using a 30% sulfonated distilledtalloel as promoter, together with sulfuric acid. Part of the ore wasthoroughly deslimed in accordance with good ore dressing practice, partwas partially deslimed, and part was not deslimed at all. The resultsappear in the following table:

Assay LbsJton used Per cent Pmduct :551:13? Per Per cent cent PromoterH1804 2 f Essential] completely deslimed:

Oalc. ad. 100. 00 14. 33 100. 00 6. 84 36. 7s 14. 99 19. 54 67. 20 9. 7478. 01 1. 60 1. 50 8. 76

It will be apparent that while desliming is desirable it need not becarried to an extreme degree. In each case the amount of reagentemployed was that which gives optimum results, and it will be apparentthat when the ore is undeslimed inferior grade is obtained, even thougha considerably increased amount of reagent is used.

Example 8 The ore of Example 1 was used, but part of the ore wasconditioned at 65% solids and part at 22% solids. The reagents used were1.62 lbs. per ton of 30% sulfonated distilled talloel, 1.62 lbs. per tonsulfuric acid and 3.05 lbs. per ton fuel oil. The results appear in thefollowing table:

Concentrate r Pulp density per cent cent Fe pe Tamng solids Assay AssayDistrib. peii cent pH Conditioning Flotation It will be apparent thatconditioning at high solids appears to be necessary in order to getmaximum results. This is in line with our experience with sulfonatedhydrocarbons as promoter reagents and in this respect the presentinvention does not depart from optimum conditions set out in our twocopending applications referred to above.

Example 9 Assay P t el'cen Product trib weight Percent Percent of Fe Itwill be apparent that with a soft iron ore considerable secondary shineis formed by scrubbing. However, in many cases it is desirable to removethis slime as it will be noted that an excellent recovery was made, the69.82% actually amounting to over of the iron in the flotation feed,some 23% of the iron in the original sample being rejected as slime. Thedesirability of scrubbing to remove secondary slimes is largelydependent on the nature of the surface of the ore particles and isdesirable with some ores and not with others. By comparing the resultsof Example 9 with those obtained in Example 7 on essentially completelydeslimed ore, it will be apparent that considerable saving in reagentswas obtained by the use of the scrubbing procedure.

Example 10 The procedure of Example 1 was followed but the varioussulfonated talloels were used in three portions, immediately afterpreparation, one hour after preparation, and 24 hours after preparation.The sulionated talloel for the first series of three tests was 30%sulfonated distilled talloel, while that used for the second and thirdseries was 50% sulfonated refined talloel. In the third series thesulfonated talloel was diluted as soon as made and was allowed to standin the form of a 7.5% aqueous solution. The reagent amounts in the caseof the first two series were 1.62 lbs. per ton and in the last series3.24 lbs. per ton. Results appear in the following table:

Concentrate Lbalton pen tFe Rglntaillng Whenused Assay mso. gi AssayDistrib. percent pH Immediately after preparation 1.62 4.07 57.20 91.771.07 2.65 1 hour after preparation 1.62 4.07 50.59 90.67 1.31 2.7 24hours after preparat on 1.62 4.07 60.43 46.77 6.09 2.6 Immediately afterreparation 1.62 5.07 57.64 93.83 0.83 2.6 1 our alter prepstation 1.626.07 68.40 92.8 0.95 2.65 24 hours after preparation 1.62 5.07 42.993&16 9.25 2.7 Immediately after preparation 1.02 5.07 53.92 91.46 0.9525 24hours alter preparation 1.62 5.07 52.66 89.07 1.07 2.6

It will be apparent that the sulfonated talloel keeps for a suilicienttime to permit satisfactory feeding in commercial operations, but doesnot keep for a day. However. if it is desired to keep the talloel forlonger periods this may be effected by dissolving the sulfonated talloelin water as soon asitisprepared.

The above results were obtained with sulfonated talloels which had notbeen neutralized, and these remarks are not completely applicable toneutralized or partially neutralized talloels.

Example 11 no discernible diflerence between natural and synthetictalloels of the same composition.

The expression oxidized iron ores" is used herein in its commonlyaccepted meaning to include not only iron oxide ores such as thosecontaining magnetite, hematite, etc., but also hydroxides, carbonate,etc.

We claim:

1. A method of beneficiating oxidized iron ores by froth flotation whichcomprises subjecting the ore to froth flotation in the presence of aneffective amount of a collector containing as its essential collectingconstituent sulfonated talloel including an eifective amount of an acidsubstance the anion of which is a constituent of an acid having adissociation constant of at least and which does not adversely effectflota- Lbs Concentrate Pr Mn Feed per cent Fe omoter my need, Source ofare N at Fuel Fe H5804 on Assay Dlstrib.

3. 48 2. 64 4. es Minnesota-aw tailing, p 7 116111! and quartz 43. as68. 67 80. 86 -2 2. 1.1 2. l1 3. 72 ta-a tag nlte (an. &1;

talnin r ma 3 17 4.22 5. Nandvq mytinfi 22.76 54.45 96.29 0-2 ew one---a mans c on coni 2 w z w a. a eeni ra n a. 64.22 68.43 06. 81 0-1 ewone amsgne m c table con oentrate 61. 47 70. 32 76. 41

2.64 2.64 4.96 Minnesota-a tsconite ore, contsining hematite anduarts...- 87.88 56.89 vase 0-2 2. 64 2. ll 4. 9 Minnesota-a washer re ctfrom a hematite o so. 28 50. 83 89. 71 4 2. 11 2. 11 4.46 M ta-a washertailing, con L 60 L t a tuini ng h tiie W- 18.88 I 54.69 0?. 07 0-1 ewarse -an ore con martlto aid quarts 22. 75 07.09 91. 61 0-2 I Refractorydue to locking of Fe and'SiO, in due alaes.

It will be apparent that acceptable results are obtained with variousiron ores, the less refrw tory ores giving commercial grade products andeven the highly refractory ores giving products which can be utilized.

While the best results are obtained when sulfonated talloels are used inconjunction with other acid substances such as sulfuric acid, fairresults are obtainable with some sulfonated talloels particularly whenassociated with unsulfonated oils without additional acid. It isdifficult to determine whether the action may be due in part to some ofthe sulfonated talloel acting as an acid agent and some as a promoter.However, the invention is not limited in its broadest aspects to the useof an added acid substance although this constitutes the preferredprocedure and in most cases gives the best commercial results.

Throughout the specification and claims natural talloel has beendescribed, that is to say the mixture of resin and unsaturated fattyacids which is obtained by acidification of black liquor soap from thesulfate paper pulp process. In certain. localities where talloel is notreadily available synthetic mixtures have been made up of resin acidsand unsaturated fatty acids which behave in the same manner as naturaltalloel and which are referred to in the art as synthetic talloel. Theterm as used in the present speciflcation and claims is intended tocoverthe mixture of resin and unsaturated fatty acids regardless of themethod by which this mixture is produced and. therefore, is intended tocover synthetic talloels as well as natural talloels. From thestandpoint of froth flotation there is tion whereby a concentrate isobtained relatively rich in iron mineral and a tailing relatively poorin iron.

2. A method of beneflciating oxidized iron ores by froth flotation whichcomprises conditioning the ore at high solids with a reagent containingsulfonated talloel as its essential collecting conby froth flotationwhich comprises conditioning the ore at high solids with a reagent.containing sulfonated talloel as its essential collecting constituentand an effective amount of sulfuric acid, diluting the conditioned oreto flotation density and subjecting it to froth flotation to produce aconcentrate relatively rich in iron mineral and a tailing relativelypoor in iron.

4. A method according to claim 1 in which the reagent is associated withan unsulfonated oil.

5. A method according to claim 2 in which the reagent is associated withan unsulfonated oil.

6. A method according to claim 3 in which the reagent is associated withan unsulfonated oil.

'I. A method according to claim 1 in which the reagent is associatedwith unsulfonated talloel.

8. A method according to claim 2 in which the reagent is associated withunsulfonated talloel.

9. A method according to claim 3 in which the reagent is associated withunsulfonated talloel.

10. A method according to claim 1 in which the reagent is associatedwith an unsulionated glyceride oil.

11. A method according to claim 2 in which the reagent is associatedwith an unsultonated glyceride 011.

12. A method according to claim 3 in which the reagent is associatedwith an unsulfonated 10 glyceride oil.

13. A method according to claim 1 in which the reagent is associatedwith an unsultonated hydrocarbon oil.

14. A method according to claim 2 in which the reagent is associatedwith an unsuitonated hydrocarbon oil.

15. A method according to claim 3 in which the reagent is associatedwith an unsuitonated hydrocarbon oil.

ROBERT B. BOOTH. EARL C. HERKENHOFF.

